CN111420684A - 一种合成气直接制乙醇的催化剂及应用 - Google Patents
一种合成气直接制乙醇的催化剂及应用 Download PDFInfo
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 97
- 239000003054 catalyst Substances 0.000 title claims abstract description 56
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 23
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 21
- MHWZQNGIEIYAQJ-UHFFFAOYSA-N molybdenum diselenide Chemical compound [Se]=[Mo]=[Se] MHWZQNGIEIYAQJ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims description 17
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
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- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 claims description 3
- 229910001950 potassium oxide Inorganic materials 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
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- 239000012752 auxiliary agent Substances 0.000 abstract description 3
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- 229930195733 hydrocarbon Natural products 0.000 description 6
- 150000002430 hydrocarbons Chemical class 0.000 description 6
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- 229910052799 carbon Inorganic materials 0.000 description 5
- 229910052961 molybdenite Inorganic materials 0.000 description 5
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000000446 fuel Substances 0.000 description 4
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- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
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- 238000009776 industrial production Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
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- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- BUGBHKTXTAQXES-AHCXROLUSA-N Selenium-75 Chemical compound [75Se] BUGBHKTXTAQXES-AHCXROLUSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
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- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
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- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
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- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
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- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/057—Selenium or tellurium; Compounds thereof
- B01J27/0573—Selenium; Compounds thereof
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- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
- C07C29/153—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
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Abstract
一种用于合成气直接制乙醇的催化剂,各组分的质量百分含量为:硒化钼65‑95%,助剂5‑35%。本发明涉及的催化剂总醇选择性高、总醇中乙醇含量高、适合于H2/CO比较低的合成气,具有良好的应用前景。
Description
技术领域
本发明涉及一种合成气制乙醇的催化剂及应用,具体地说,是一种用于合成气制乙醇的硒化钼催化剂及应用。
背景技术
乙醇是重要的化工原料、燃料及燃料添加剂,在化工、制药、能源等诸多领域具有十分广泛的应用。一方面,乙醇作为燃料添加剂,可以有效提高燃料燃烧效率,增加燃料辛烷值,减少CO排放;另一方面,由煤炭经合成气制得的乙醇,产品中不含N、S等元素,燃烧后不会产生NOx、SOx等污染,是一类环境友好的清洁燃料。此外,乙醇也可作为硝基喷漆、清漆、化妆品、油墨、脱漆剂等的溶剂以及农药、医药、橡胶、塑料、人造纤维、洗涤剂等的制造原料,还可以做防冻剂、粘合剂、消毒剂等。由CO催化加氢制备乙醇,不仅是C1化学研究的重要分支,也是实现煤炭资源高效、清洁利用的重要途径之一。尽管研究人员在该领域做了大量的研究工作,但目前CO催化加氢直接制备乙醇仍没有实现大规模工业化生产,其主要原因在于还没有开发出适合于工业生产的催化剂。研制性能优异、成本低廉的催化剂依然是合成气制乙醇领域研究的重点。
中国专利(201610898404.6)报道了一种由氧化铜、氧化锆、氧化钾和载体组成的合成气制乙醇催化剂。该催化剂经过还原后,在H2/CO=2,6MPa、250℃、6000h-1的条件下,CO转化率=15.8%,醇类、烃类、CO2的选择性(Cmol.%)分别为23.6、30.7、22.4,醇中甲醇、乙醇、丙醇、丁醇以及C5+醇的分布(wt.%)分别为39.2、55.7、2.4、2.3和0.7。尽管该催化剂展现出了优良的乙醇选择性,但偏高的烃类选择性依然有待优化。
贵金属铑催化剂可以在较温和的条件下高选择性的合成乙醇。中国专利(201410589965.9)报道了一种由铑、铁和氧化铝组成的合成气制乙醇催化剂,在反应温度为280℃、反应压力为3MPa、气体空速为5400h-1、H2和CO摩尔比为2的条件下,CO的转化率最高为32.5%,制备的乙醇的选择性为39.2%。但贵金属催化剂较高的成本也限制了该催化剂的进一步应用。
在诸多合成气制乙醇催化剂体系中,钼基催化剂因其具有较高的醇类选择性、优异的抗硫性能,被认为是最有前景的催化剂体系,受到了研究人员的广泛关注。美国的DowChemical公司于1986年在其申请的专利中(EP 0170973)首次报道了硫化钼基催化剂在合成气制低碳醇中的应用,该催化体系具有良好的抗硫性能,低碳醇产品含水量少,产物的醇选择性较高。国内关于合成气制低碳醇硫化钼基催化剂的专利主要有CN 1431049, CN1631527, CN 1663683, CN 108325548。其中,值得一提的是中科院山西煤化所孙予罕课题组通过向硫化钼催化剂中加入Ni、Fe、Mn、K等助剂,获得了性能优良的合成气制低碳醇催化剂,总醇选择性可达60%以上,但该催化体系主要产物是甲醇。
尽管MoS2基催化剂醇类产物选择性较高,但传统的MoS2基催化剂醇类产物以甲醇为主,通常占总醇的50%以上,这也极大地限制了MoS2基催化剂的应用前景。针对MoS2基催化剂C2+醇选择性低的问题,研究人员做了大量的研究。通常认为过渡金属(如Fe、Co、Ni)的加入,可以有效地提高MoS2基催化剂的催化活性和C2+醇选择性,但由于Fe、Co、Ni较高的加氢活性会导致大量烃类附产物的生成。同时,这些过渡金属因为会在反应过程中生成沸点较低的羰基化合物而流失,从而导致催化剂活性下降。因此,合成同时具有优异总醇选择性和乙醇选择性的催化剂在该领域仍然是一个挑战。
发明内容
本发明提供了一种乙醇选择性高、适用于较低H/C比的合成气制乙醇催化剂及其应用领域和反应工艺条件。
本发明的催化剂的组成为:硒化钼65-95 wt%,助剂5-35 wt%。其中,助剂为碳酸钾、氧化钾、氢氧化钾或醋酸钾中的一种或多种。
本发明的催化剂的应用领域为合成气制乙醇或低碳混合醇。
本发明的催化剂的使用条件为:合成气中H2/CO体积比为0.8-1.2,反应温度为300-400 ℃,反应压力为8-12 MPa,空速为1000-10000 h-1。
具体实施方式
实施例1:
将1.2359克仲钼酸铵、1.1054克硒粉和75毫升去离子水依次加入烧杯,搅拌10分钟后加入0.7944克硼氢化钠,继续搅拌10分钟后,将所得分散液转移至具有聚四氟乙烯内胆的水热釜中。将水热釜放入鼓风干燥箱,于220摄氏度下反应48小时后自然降温,得到黑色沉淀。将所得黑色沉淀水洗10次,乙醇洗2次,60摄氏度下真空干燥过夜,即得硒化钼。
将0.1837克碳酸钾溶于水后,加入0.9克硒化钼,研磨均匀后加入乙醇,60摄氏度下真空干燥3h,制得K0.75MoSe2催化剂。将制得的K0.75MoSe2催化剂压片造粒,取40-60目颗粒备用。
将上述步骤制备的K0.75MoSe2催化剂在不锈钢固定床反应器中进行催化性能评价。反应条件:温度340℃,压力10MPa,空速3000h-1,合成气V(H2):V(CO)=1。催化剂CO转化率=8.6%,醇、烃、CO2的选择性(Cmol%)分别为43.4、26.3和30.3,醇中甲醇、乙醇、丙醇、C3+醇的质量分数分别为23.2%、54.6%、17.3%和4.9%。
实施例2:
将0.2450克碳酸钾溶于水后,加入0.9克实施例1制得的硒化钼,研磨均匀后加入乙醇,60摄氏度下真空干燥3h,制得K1.0MoSe2催化剂。将制得的K1.0MoSe2催化剂压片造粒,取40-60目颗粒备用。
将上述步骤制备的K1.0MoSe2催化剂在不锈钢固定床反应器中进行催化性能评价。反应条件:温度320℃,压力10MPa,空速3000h-1,合成气V(H2):V(CO)=1。催化剂CO转化率=7.2%,醇、烃、CO2的选择性(Cmol%)分别为53.0、19.8和27.2,醇中甲醇、乙醇、丙醇、C3+醇的质量分数分别为32.8%、54.5%、10.9%和1.8%。
实施例3:
将0.2450克碳酸钾溶于水后,加入0.9克实施例1制得的硒化钼,研磨均匀后加入乙醇,60摄氏度下真空干燥3h,制得K1.0MoSe2催化剂。将制得的K1.0MoSe2催化剂压片造粒,取40-60目颗粒备用。
将上述步骤制备的K1.0MoSe2催化剂在不锈钢固定床反应器中进行催化性能评价。反应条件:温度340℃,压力10MPa,空速3000h-1,合成气V(H2):V(CO)=1。催化剂CO转化率=14.6%,醇、烃、CO2的选择性(Cmol%)分别为45.6、24.6和29.8,醇中甲醇、乙醇、丙醇、C3+醇的质量分数分别为18.5%、54.8%、20.3%和6.4%。
本发明的实施例证明,钾助剂改性的硒化钼催化剂在总醇选择性高的前提下,具有优异的乙醇选择性,是一类非常具有应用前景的合成气制乙醇催化剂。
Claims (4)
1.一种用于合成气直接制乙醇的催化剂及应用,其特征在于催化剂的组成为:硒化钼65-95 wt%,助剂5-35 wt%。
2.根据权利要求1所述的催化剂,其特征在于助剂为碳酸钾、氧化钾、氢氧化钾或醋酸钾中的一种或多种。
3.根据权利要求1所述的催化剂,其特征在于催化剂的应用领域为合成气制乙醇或低碳混合醇。
4.根据权利要求1所述的催化剂,其特征在于催化剂的使用条件为:合成气中H2/CO体积比为0.8-1.2,反应温度为300-400 ℃,反应压力为8-12 MPa,空速为1000-10000 h-1。
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